Corrosion-resistant glasses for steel enamels

ABSTRACT

A cementitious composite material wherein glass-coated steel rods are positioned in a cementitious matrix. The glass composition for coating the steel reinforcing rods includes between about 33-45 weight percent SiO 2 , 13.5-19.5 weight percent B 2 O 3 , 3.5-4.6 weight percent Al 2 O 3 , 4.0-13.5 weight percent K 2 O, 5.5-15.5 weight percent ZrO 2 , 8.6-15.9 weight percent Na 2 O, 4.6-5.1 weight percent CaO, 0.6-0.7 weight percent MnO 2 , 1.0-1.0 weight percent NiO, and 1.0-1.1 weight percent CoO. The glass composition is typically in compression on the rods at ambient temperatures, has a coefficient of thermal expansion of between about 12.5 and about 13.5, and has a softening temperature of between about 585 degrees Celsius and about 600 degrees Celsius.

CROSS-REFERENCE TO RELATED APPLICATIONS

This patent application claims priority to co-pending U.S. patentapplication Ser. No. 12/623,236, filed on Nov. 20, 2009, which claimedpriority to then U.S. Provisional Patent Application Ser. No.61/199,901, filed Nov. 21, 2008.

GRANT STATEMENT

The invention was made in part from government support under Grant No.W911NF-07-2-0062 from the Department of the Army. The U.S. Governmenthas certain rights in the invention.

TECHNICAL FIELD

The present invention relates to structural materials and, moreparticularly, to a new and improved glass composite developed forcoating steel elements for reinforcing concrete structures.

BACKGROUND

One material very commonly selected for large-scale constructionprojects is reinforced concrete (RC). Several years ago, the Army Corpsof Engineers discovered that the use of a modified vitreous enamelimproved the bond strength, and, possibly, the corrosion resistance ofthe steel rods reinforcing the concrete. The enamel consisted of a glassmatrix embedded with reactive ceramic particles. The glass compositionwas designed to strongly adhere to the steel, and the reactive particleswere imbedded to chemically react with the surrounding cement to formanother strong bond.

The materials used for these initial tests included commercialalkali-resistant groundcoat enamels for steels used in a variety ofconsumer and industrial applications. The typical compositional rangesfor such enamels are summarized below as Table 1.

TABLE 1 Compositional ranges for typical alkali-resistant groundcoatsConstituent Range (wt %) Silicon dioxide SiO₂ 40-45 Boron oxide B₂O₃16-20 Na oxide Na₂O 15-18 K oxide K₂O 2-4 Li oxide Li₂O 1-2 Ca oxide CaO3-5 Aluminum oxide Al₂O₃ 3-5 Zr oxide ZrO₂ 4-6 Mn dioxide MnO₂ 1-2 Nioxide NiO 1-2 Cobalt oxide Co₃O₄ 0.5-1.5 Phosphorus oxide P₂O₅ 0.5-1  

The ratio of the Na₂O, B₂O₃, and SiO₂ components, as well as theaddition of other alkali (K₂O and Li₂O) and alkaline earth oxides (CaO),have the greatest effect on the thermal properties of the glass.Constituents like Al₂O₃ are added to improve the corrosion-resistance ofthe glass. ZrO₂ (and P₂O₅) is usually added to an enamel as an opacifierto affect the visual appearance of the coating. However, zirconia hasthe added advantage of improving the chemical resistance of silicateglasses to attack by alkaline environments. Alkaline-resistant silicateglass fibers developed for reinforcing cement composites typicallycontain 10-20 wt % ZrO₂, and a protective coating of Zr-oxyhydroxideforms on the glass surface when exposed to an alkaline environment,further impeding corrosion. Transition metal oxides, like MnO₂, CO₃O₄,and NiO, are added to enamels to aid bonding to the substrate.

In general, these materials are sodium-borosilicate glasses modifiedwith various constituents to tailor thermal and chemical properties.However, the conventional groundcoat enamels (such as the ones listed inTable 1) are designed with thermal properties tailored for the steelalloys used in commercial and industrial applications. Therefore, thereis a need to provide a new and improved glass composite having physicaland chemical properties specifically suited for coating the reinforcingsteel used in RC structures, specifically with thermal propertiestailored for steel alloys used in RC structures and with chemicalproperties designed for alkaline cement environments. There is likewisea need for reinforcing steel members having corrosion resistant coatingsbetter matched to the physical properties of the underlying steel so asto better adhere thereto. Finally, there remains a need for an improvedsteel-concrete composite material wherein the steel phase is moresecurely bonded within the concrete matrix phase to yield a toughercomposite material. The present novel technology addresses these needs.

SUMMARY

The present novel technology relates to a glass composition havingthermal expansion and corrosion resistance desirable for coating steelrods used in RC concrete applications. The glass composition for coatingsteel reinforcing rods typically includes SiO₂ present in between about33 and about 45 weight percent; B₂O₃ present in between about 13.5 andabout 19.5 weight percent; Al₂O₃ present in between about 3.5 and about4.6 weight percent; K₂O present in between about 4.0 and about 13.5weight percent; ZrO₂ present in between about 5.5 and about 15.5 weightpercent; Na₂O present in between about 8.6 and 15.9 weight percent; CaOpresent in between about 4.6 and about 5.1 weight percent; MnO₂ presentin between about 0.6 and about 0.7 weight percent; NiO present inbetween about 1.0 and about 1.1 weight percent; and CoO present inbetween about 1.0 and about 1.1 weight percent. The glass compositionhas a coefficient of thermal expansion of between about 12.5 and about13.5 and has a softening temperature of between about 585 degreesCelsius and about 600 degrees Celsius.

One object of the present novel technology is to provide an improvedsteel reinforced concrete system including the same. Related objects andadvantages of the present novel technology will be apparent from thefollowing description.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a cutaway perspective view of a steel rod coated with avitreous material according to a first embodiment of the present noveltechnology.

FIG. 2A is a perspective view of a first plurality of steel rodsaccording to FIG. 1 embedded in a cementitious material to yield a firstcomposite material according to a second embodiment of the present noveltechnology.

FIG. 2B is an enlarged partial view of one of the embedded rods of FIG.2A.

FIG. 3A is a perspective view of a second plurality of steel rodsaccording to FIG. 1 embedded in a cementitious material to yield asecond composite material according to a second embodiment of thepresent novel technology.

FIG. 3B is an enlarged partial view of one of the embedded rods of FIG.2A.

FIG. 4 shows weight changes for glasses after up to 28 days in alkalineLawrence Solution at 80° C.

FIG. 5 shows the comparisons of average bond strengths (in MPa) forsteel pins embedded in mortar after up to 60 days.

FIG. 6 is a graphical representation of the change in linear dimensionvs. temperature of a steel rod and two vitreous coating compositions forthe coated steel rods of FIG. 1.

DETAILED DESCRIPTION

For the purposes of promoting an understanding of the principles of thenovel technology and presenting its currently understood best mode ofoperation, reference will now be made to the embodiments illustrated inthe drawings and specific language will be used to describe the same. Itwill nevertheless be understood that no limitation of the scope of thenovel technology is thereby intended, with such alterations and furthermodifications in the illustrated device and such further applications ofthe principles of the novel technology as illustrated therein beingcontemplated as would normally occur to one skilled in the art to whichthe novel technology relates.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs.

In one embodiment, steel reinforcing rods 10 are coated with the novelglass composition 20 to yield coated reinforcing rods 30. The glasscoating 20 is particularly suitable for coating the steel alloys used inthe rods 10, as the glass coating 20 typically has a coefficient ofthermal expansion close to but lower than that of the steel rods 10,such that the glass coating 20 is maintained in compression. Further,the glass coating 20 is substantially more corrosion resistant than theconventional enamel coatings known in the art. Specifically, the thermalproperties of the glass coatings are tailored for the steel alloys usedin RC structures, which have different thermal expansion coefficientsthan the alloys used in commercial and industrial applications for whichthe conventional groundcoat compositions were designed. Typically, thesteel alloys used in the rods 10 are ASTM A 615, 706, 955, 996 or thelike, which typically have thermal expansion coefficients of from about14 ppm/° C. to about 17 ppm/° C. The glass coating 20 typically has athermal expansion coefficient of between about 12.5 ppm/° C. and about13.5 ppm/° C. at ambient temperatures.

In particular, the borate-to-silicate ratio and the fraction and type ofalkali oxide of the coatings 20 has been optimized to yield coatings 20characterized by greater CTE to improve the thermomechanicalcompatibility with typical reinforcing steel. In other words, the CTE ofthe glass coatings 20 has been raised to be closer to that of typicalsteel rebars 10 while remaining slightly lower than the steel CTE, suchthat the glass coating 20 is put into compression 20 but not so much sothat it fails and disengages therefrom. Further, this CTE matching wasaccomplished without sacrificing chemical durability of the glasscoating 20. Thus, by better matching the thermomechanical properties ofthe glass coatings 20 to the steel members 10, the glass coatings 20 areless prone to failure due to stresses arising from thermal cycling andthus remain on the steel members 10 where they can participate in thebonding process with a surrounding cementitious matrix material.

Additionally, the corrosion resistance of the glass coatings 20 isespecially attractive in alkaline environments. The glass coatings 20typically includes substantially increased concentrations of CaO, K₂Oand, more typically, ZrO₂ at levels substantially greater than thetypical enamel compositional ranges to provide increased corrosionresistance of the glass coated rods 30 in alkaline environments.

In some embodiments, as seen in FIGS. 2A-3B, cement-reactive particles35, such as calcium silicate, are dispersed in the glass coatings 20 toenhance bonding with a cement matrix 40 to result in a steel-reinforcedconcrete composite material 50 having increased bond strength betweenthe coated rods 30 and the cement matrix 40. Such a material 50 willexhibit a substantially increased pull-out strength and be inherentlytougher. Alternately (or additionally), metal particles 45 such as zincmay be dispersed in the glass coating 20 to act as sacrificial anodesfor further protecting the steel rods 30 from the corrosive effects ofthe cementious matrix 40. Still alternately, such sacrificial anodeparticles 45 may be added directly to the cement, either throughout orpreferentially near the steel rods 10, to react locally with thecorrosive cementitious matrix 40 to divert its attack on the steel rods10. As they are corroded, the sacrificial metal particles 45 will expandto provide both physical as well as chemical protection, chemicallyreacting with corrosives and physically blocking the corrosion pathways.

Table 2 shows the compositions of several embodiments of the glasscoating 20, along with test results of the dilatometric softening pointand the CTE, designated ARE-1 through ARE-5. For comparison, thecomposition and properties of a standard (conventional) alkali-resistantgroundcoat composition is presented and designated ARG.

TABLE 2 Comparision between the novel glass coating compositions and ARGwt % ARE-1 ARE-2 ARE-3 ARE-4 ARE-5 ARE-11 ARG SiO₂ 44.5 43.4 39.7 42.033.2 39.3 44.0 B₂O₃ 17.9 14.4 14.0 13.9 19.2 13.0 19.3 Na₂O 15.9 15.515.1 8.9 8.6 8.3 15.8 K₂O 4.3 4.2 4.1 13.5 13.0 12.6 2.8 CaO 5.1 5.0 4.84.8 4.6 4.5 4.7 CaF₂ Al₂O₃ 3.6 3.8 3.7 3.6 3.5 3.4 4.6 ZrO₂ 5.6 10.910.6 10.6 15.3 9.9 5.3 MnO₂ 0.7 0.6 0.6 0.6 0.6 0.6 1.5 NiO 1.1 1.1 1.11.1 1.0 1.0 1.0 CoO 1.1 1.1 1.1 1.1 1.0 1.0 0.9 P₂O₅ 0 0 0 0 0 6.4 SoftTemp (° C.) 600 586 600 600 594 610 576 CTE (ppm/° C.) 13.5 12.9 12.512.9 12.7 10.8 12.2

FIG. 4 shows the change in weight for glass samples after up to 28 daysat 80° C. in Lawrence solution (pH=13). The K₂O and ZrO₂ contents of theARE-series glass coatings 20 are each, respectively, greater than thoseof the ARG composition, and the weight changes of ARE compositions 2 and5 are respectively less than that of the ARG glass.

In another embodiment, reinforced concrete 50 was prepared by thepouring wet concrete over coated rods 30 and allowing the concrete todry and cure to define a concrete matrix 40, yielding a reinforcedconcrete composite material 50. The bonding of the coated rods 30 in theconcrete matrix 40 was analytically measured.

A series of pull-out tests was conducted to assess the bond strengths ofthe embedded coated rods 30 with several compositional embodiments ofthe glass coating material 20. The results of pull-out testing are shownin FIG. 5.

Preparation of Test Mortar.

Uncoated steel rods 10 and coated rods 30 were embedded in a mortarprepared using the guidelines presented in ASTM C109, Standard Methodfor Determining Compressive Strength of Hydraulic Mortars. Theproportion of the standard mortar was one part cement (Type I) to 2.75parts of standard graded sand. The water-to-cement ratio was maintainedat 0.485. Test cylinders were prepared for each mortar batch and testedto investigate the compressive strength at 7 and 30 days.

Preparation and Testing of Embedded Rods for Pull-Out Testing.

Each uncoated 10 and glass coated test rod 30 was inserted in a 50.8-mmin diameter, 101.6-mm long plastic cylinder mold filled with freshmortar. The respective rods 10, 30 were clamped at the top so that a63.5-mm length of each respective rod 10, 30 was under the mortar; forthe coated rods 30, the portion under mortar was glass coated. Eachcylinder was tapped and vibrated to remove entrapped air and also toconsolidate the mortar. The samples were kept in a 100% humidityenvironment at room temperature and cured, with curing times rangingfrom 7 days and to 60 days. After curing, the test cylinders werede-molded and the mounted in the test apparatus and the force requiredto pull each respective rod 10, 30 out of the mortar was measured usingan Instron Model 4469 Universal Testing Machine.

The testing pin-pull results for steel after up to 60 days in mortarindicate that the bond strength of the uncoated pins decreases fromabout 4 MPa to about 2.2 MPa between seven days and 28 days of curing.This is consistent with reports in the literature for decreasing bondstrength between cement paste and reinforcing steel with increasingcuring time age, particularly from 1 to 14 days. However, due thehydration reaction of cement with the reactive Ca-silicate particlesused for the glass coated samples 30, these bond strengths increase from1.2 MPa to 6.60 kPa with an increase of curing time from three days to60 days. Further, glass coated steel pins 30 with reactive calciumsilicate have about three times the bond strength of bare steel pinsafter 60 days in cement.

Steel-reinforced concrete composite material 50 benefitting fromincreased bond strength and decreased degradation of the steel 10 fromcorrosive attack by the concrete matrix 40 give rise to a number ofuses, such a structural material for floors and decking, hardened orreinforced civilian and military structures, sewage pipe, geotechnicalanchorages, and the like. Further, the strong bond formed between theglass-coated steel 30 (with or without calcium silicate particles or thelike dispersed therein as bonding enhancers) and the cementitiousmaterial 40 enables design options such as concrete-filled steel tubesor casings.

Further, the glass composition may be optimized to be self-sealing. Asthe glasses have relatively low softening temperatures, they are wellsuited for low temperature applications, such as retrofit andremediation applications. Additionally, glass-tape composites may bemade with these compositions that may be wrapped around steel membersand then fused thereto via the direct application of heat, such as byinduction or a torch, to provide corrosion protection and/or an enhancedbonding surface.

Referring to FIG. 6, the change in linear dimension as a function oftime is plotted for both a steel rod 10 and for two coating compositions(ARE-4 and ARE-11P). The rod 10 has a measured CTE of 16.9 ppm/° C.,while the ARE-4 composition has a CTE of 12.9 ppm/° C. and the ARE-11Phas a CTE of 10.8 ppm/° C. The CTE of the rod 10 is substantiallyconstant over a temperature range of about 100 to about 700 degreesCelsius, while the CTE's of the glass coating compositions aresubstantially constant over ranges of between about 200 to about 450degrees Celsius. Both compositions appear to beging to soften at about500 degrees Celsius, resulting in a change in CTE in the 500 to 600degree Celsius range.

The desired properties of the novel glass composite include 1) acoefficient of thermal expansion (CTE) that is more compatible with thesteel alloy that is to be coated, 2) a softening temperature that isrelatively low (<700° C.) to ensure low processing temperatures that donot degrade the mechanical properties of the steel, and 3) outstandingcorrosion-resistance to the alkaline environment of wet cement. Thenovel glass composite comprises at least 4.0% (wt) K₂O and at least 5.6%(wt) ZrO₂, with about 4-20% (wt) of K₂O, and/or about 5-20% (wt) ofZrO₂, whereas both K₂O and ZrO₂ are significantly increased compared tothe conventional groundcoats.

While the novel technology has been illustrated and described in detailin the drawings and foregoing description, the same is to be consideredas illustrative and not restrictive in character. It is understood thatthe embodiments have been shown and described in the foregoingspecification in satisfaction of the best mode and enablementrequirements. It is understood that one of ordinary skill in the artcould readily make a nigh-infinite number of insubstantial changes andmodifications to the above-described embodiments and that it would beimpractical to attempt to describe all such embodiment variations in thepresent specification. Accordingly, it is understood that all changesand modifications that come within the spirit of the novel technologyare desired to be protected.

We claim:
 1. A method for producing composite structural materialcomprising in combination: providing a cementitious matrix; positioninga plurality of steel reinforcing rods positioned in the cementiousmatrix; and substantially encapsulating each respective steelreinforcing rod in a vitreous shell; and substantially encasing theplurality of steel reinforcing rods in the cementitious matrix; whereineach respective steel reinforcing rod has a coefficient of thermalexpansion of between about 14 ppm/° C. and about 17 ppm/° C.; andwherein each respective vitreous shell has a composition consistingessentially, in weight percent, of about 33-45% SiO₂, 3.5-4.6% Al₂O₃,13.5-19.5% B₂O₃, 4-13.5% K₂O, and 5.5-15.5% ZrO₂; and wherein eachrespective vitreous shell has a coefficient of thermal expansion betweenabout 12.5 ppm/° C. and about 13.5 ppm/° C.
 2. The composite structuralmaterial method of claim 1 and further comprising a plurality of calciumsilicate particles distributed throughout each respective vitreousshell.
 3. The composite structural material method of claim 2 whereinthe calcium silicate particles are bonded to the cementitious matrix. 4.The composite structural material method of claim 3 wherein thecementitious matrix is Portland cement.
 5. The composite structuralmaterial method of claim 2 wherein the bond strength of the steelreinforcing rods in the cementitious matrix increases over time.
 6. Thecomposite structural material method of claim 1 and further comprising aplurality of zinc particles distributed throughout each respectivevitreous shell.
 7. A method of reinforcing concrete, comprising: coatinga plurality of steel reinforcing members with thin glass layers, whereinthe respective steel reinforcing members have a first coefficient ofthermal expansion and wherein the respective thin glass layers have asecond coefficient of thermal expansion substantially matching the firstcoefficient of thermal expansion; and forming a cementitious matrixaround the plurality of steel reinforcing members; wherein the glasslayers have a composition consisting essentially, in weight percent, ofabout 33-45% SiO₂, 3.5-4.6% Al₂O₃, 13.5-19.5% B₂O₃, 4-13.5% K₂O, and5.5-15.5% ZrO₂.
 8. The method of claim 7, wherein the steel reinforcingmembers have a composition selected from the group including ASTM A615,ASTM A706, ASTM A955 and ASTM A996.
 9. The method of claim 7, whereinthe glass layers have a coefficient of thermal expansion between about12.5 and 13.5 ppm per degree Celsius.
 10. The method of claim 7, whereinthe glass layers contain about 10.5 to about 15.5 weight percent ZrO₂and between about 13.0 and about 13.5 weight percent K₂O.
 11. The methodof claim 7, wherein the thin glass layers further comprise a pluralityof calcium silicate particles distributed therethrough and wherein thecalcium silicate bonds with the cementitious matrix.
 12. The method ofclaim 4, wherein the thin glass layers further comprise a plurality ofmetal particles distributed therethrough; and wherein the metalparticles function as sacrificial anodes in a cementitious environment.13. The method of claim 12 wherein the metal particles are zinc.
 14. Amethod of making a reinforced cementitious composite material,comprising: substantially encapsulating each of a plurality ofrespective steel reinforcing rods in a respective vitreous shell;distributing bond-enhancing particles throughout each respectivevitreous shell; positioning the encapsulated steel reinforcing rods; andsubstantially encasing the plurality of steel reinforcing rods in acementitious matrix; wherein each respective steel reinforcing rod has acoefficient of thermal expansion of between about 14 ppm/° C. and about17 ppm/° C.; and wherein each respective vitreous shell has acomposition selected from the group consisting essentially, in weightpercent, of about 33-45% SiO₂, 3.5-4.6% Al₂O₃, 13.5-19.5% B₂O₃, 4-13.5%K₂O, and 5.5-15.5% ZrO₂; and wherein each respective vitreous shell hasa coefficient of thermal expansion between about 12.5 ppm/° C. and about13.5 ppm/° C.
 15. The method of claim 14 wherein the bond-enhancingparticles are metallic; and wherein the metallic bond-enhancingparticles act as sacrificial anodes.
 16. The method of claim 15 whereinthe metallic bond-enhancing particles are zinc.
 17. The method of claim14 wherein the bond-enhancing particles are calcium silicate; andwherein the calcium silicate bond-enhancing particles bond with thecementitious matrix.
 18. The method of claim 14 wherein thebond-enhancing particles include both calcium silicate particles andmetallic particles.